Producing perchloric acid by irradiation



PRODUCING PERCHLORIC BY IRRADIATIUN I William A. Sandberg, OakPark, Ted-A. Erikson,10alt Lawn, and Charles H. Riesz, Chicago, 11]., assignors,by mesne assignments, to theUnited States of America s as represented bythe Secrctaryof the Navy No Drawing. Application June 12,1957

- Serial No. 665,361 V 3 Claims. or. 204-1257 Applicants have discoveredthat the presence of water vapor'in the reaction mixturespeeds thereaction, and causes the formation of perchloric acid,'avoiding theformation of lower chlorine oxides and subsequent lower chlorine acids.1 1

A suitable procedure for practicing the present 1nven,

tion consists of evacuating a reactor, which then is filled with watervapor at its vapor pressureat room temperature, i.e., at 24 millimetersof mercury pressure; Gaseous ozone then is added to the reactor to apressureof 211 chlorine in' the presence of gaseous water to radiationat. a wavelength of 2537 Angstroms with permissible ,wavelength {spreadbetween 1800 Angstrorhsfand 400 millimeters of. mercury pressure.Gaseousbhlorine is I added to the reactor next, to a total pressure of'39 6'mi1limeters.of'mercury'pressure. r p

, A'mercury-vapor bulb immersed in therea'ctoncon g taining the mixtureof. chlorine, ozone, andwater'in gaseousstate, is excited with a 27:12megacycle'radio 'fre' queucy current, by means of a suitable radiofrequency generator. A mercury-vapor bulbihas been used andis'satisfactory, which was ratedbjythe' manufacturer'to be '85 percent 2537Angstroms. The r'emainder'of theoutput of this bulb comprisedwavelengths within the range from 1800 Angstroms to 4000 Angstroms, andabout I percent of the output was inthe visible range. The

described process of irradiation was continued for three action vesselin liquid oxygen The non-condensable material was'removed by means of avacuum pump, leaving perchloric acid as the contents of the reactor.

United States Ptmo oxygen, and the non-condensed remaining gas was 7'ice pumped oif in the'manner previously: described.

Production of pcrchloric'acid was verified by flushing out thecondensate remaining in the reactor with water,- and neutralizing theresultant aqueous solution. Analysis of the neutralized solution yielded0.0029 gram of sodium chloride and .078 gram of sodium perchlorate.

' The original ozone may be diluted with oxygen. I It is 4000 Angstromsmay be used for the operationiof irradiai tion. Employing wavelengthsfor irradiation within the minutes. A halt in pressure increase wasobserved after 1 Pursuing the reaction further, and following the" de-"scribed pumping operation, applicant allowedthe material contained inthe reactor. to evaporate,-,adding "an-'' other charge of gaseous ozonetothe resultant mixture until'a gaseous ozone pressure was attained of413mmmeters of mercury pressure. This mixture was irradiated again forthree minutes. The operation of condensation then was repeated byimmersing'the reaction vessel in 1 523,263- Cannot; Jury-117,189: I vCotton Sept. 14, 1954f 2,762,768 C ier Sept. 11, 1956 In the abovedescribed process for producing pergaseous water must be present in anyevent for hydration.

not requisitethat the irradiation must be continuous; the

1. irratiation can be interrupted without atfecting there action. 1

As establishedv hereinbefore by actual operation, wave- 1 lengths-withinthe range between 1800 Angstroms and limits of'1800 Angstroms and200*Angstrorns, the reaction maybe carried out-by forthe'gaseous ozone.

f Obviously many modifications and variationsof the present inventionare possible'in the light of the above teachings. It istherefore to' beunderstood that within the scope'of the appended claims the inventionmaybe practiced otherwise than V as specifically described. We claim: '1

l1. TheJartof'producing perchloric-acid which com- 7 prisess'ubjectin'gamixture of gaseous ozoneand gaseous Angstroms, said'water vapor being atits vapor pressureat and 2000 Angstroms.

3. The process of producing perchloric' acid which. I

comprises evacuating a reactor, filling the reactor with watervvapor atits vapor pressure at room'temperature, adding gaseous ozone to, apressure of about 211 milliimeters, 'addinggaseous chlorine to a totalpressure of about '39 6 millimeters, exciting such gaseous mixture withradiation at *a wavelength of 2 735; Angstroms with permis'siblewavelength spread between 1800 Angstromsand 4000Angstroms untilreaction'abates, and. condensing the product by immersing the ReferencesCited in the filesofthis patent ,UNITED STATES PATENTS 7 2,925,368Patented Feb. 16, 1960:

substituting gaseous oxygen reaction vessel in liquid

1. THE ART OF PRODUCING PERCHLORIC ACID WHICH COMPRISES SUBJECTING AMIXTURE OF GASEOUS OZONE AND GASEOUS CHLORINE IN THE PRESENCE OF GASEOUSWATER TO RADIATION A A WAVELENGTH OF 2537 ANGSTROMS WITH PERMISSIBLEWAGELENGTH SPREAD BETWEEN 1800 ANGSTROMS AND 400 ANGSTROMS, SAID WATERVAPOR BEING AT ITS VAPOR PRESSURE AT ROOM TEMPERATURE, SAID GASEOUSOZONE BEING ADDED TO A PRESSURE OF ABOUT 211 MILLIMETERS, AND SAIDGASEOUS CHLORING BEING ADDED TO A TOTAL PRESSURE OF ABOUT 396MILLIMETERS.